Materials for electronic devices

ABSTRACT

The present invention relates to compounds of the formula (I), to the use of compounds of the formula (I) in electronic devices and electronic devices comprising one or more compounds of the formula (I). The invention furthermore relates to the preparation of the compounds of the formula (I) and to formulations comprising one or more compounds of the formula (I).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. §371)of PCT/EP2011/003484, filed Jul. 12, 2011, which claims benefit ofGerman application 10 2010 033 548.7, filed Aug. 5, 2010 which are bothincorporated by reference.

The present invention relates to compounds of the formula (I) and to theuse of compounds of the formula (I) in electronic devices. The inventionfurthermore relates to electronic devices, preferably organicelectroluminescent devices (OLEDs), comprising one or more compounds ofthe formula (I). The invention again furthermore relates to thepreparation of compounds of the formula (I) and to formulationscomprising one or more compounds of the formula (I).

The structure of organic electroluminescent devices (OLEDs) in whichorganic semiconductors, such as the compounds according to theinvention, are employed as functional materials is described, forexample, in U.S. Pat. No. 4,539,507, U.S. Pat. No. 5,151,629, EP 0676461and WO 98/27136.

The emitting materials employed here are increasingly organometalliccomplexes which exhibit phosphorescence instead of fluorescence (M. A.Baldo et al., Appl. Phys. Lett. 1999, 75, 4-6). For quantum-mechanicalreasons, an up to four-fold energy and power efficiency is possibleusing organometallic compounds as phosphorescence emitters.

In general, there is still a need for improvement, for example withrespect to efficiency, operating voltage and, in particular, lifetime,in OLEDs, in particular also in OLEDs which exhibit triplet emission(phosphorescence). This applies, in particular, to OLEDs which emit inthe relatively short-wave region, for example green.

The properties of phosphorescent OLEDs are determined not only by thephosphorescent dopants employed. In particular, the other materialsused, such as matrix materials, hole-blocking materials,electron-transport materials, hole-transport materials and electron- orexciton-blocking materials, are also of particular importance here.Improvements in these materials can thus also result in significantimprovements in the OLED properties. There is also still a need forimprovement in these materials for fluorescent OLEDs.

Matrix materials for phosphorescent dopants which are known in the priorart are, inter alia, carbazole derivatives, for examplebis(carbazolyl)biphenyl. The use of ketones (WO 2004/093207), phosphineoxides and sulfones (WO 2005/003253) is furthermore known as matrixmaterials for phosphorescent dopants. Metal complexes, for example BAIqor bis[2-(2-benzothiazole)phenolate]zinc(II), are also used as matrixmaterials for phosphorescent dopants.

However, there continues to be a demand for alternative matrix materialsfor phosphorescent dopants, in particular those which effect animprovement in the performance data of the electronic devices.

Furthermore, the provision of novel hole-transport and hole-injectionmaterials is of interest. Hole-transport and injection materials whichare known in the prior art are, inter alia, arylamine compounds.Materials of this type based on indenofluorenes are disclosed, forexample, in the applications WO 2006/100896 and WO 2006/122630.

However, the known hole-transporting materials frequently have lowelectron stability, which reduces the lifetime of electronic devicescomprising these compounds. Furthermore, improvements are desirable withrespect to the efficiency of fluorescent organic electroluminescentdevices and the lifetime, especially in the case of blue-fluorescentdevices.

The provision of novel electron-transport materials is likewisedesirable since the properties of the electron-transport material exerta significant influence on the above-mentioned properties of the organicelectroluminescent device. In particular, there is a demand forelectron-transport materials which simultaneously result in goodefficiency, a long lifetime and a low operating voltage.

It would be desirable here to have available electron-transportmaterials which result in better electron injection into the emittinglayer, since an electron-richer emission layer is accompanied by betterefficiency. In addition, better injection enables the operating voltageto be reduced.

The object of the present invention is thus in summary the provision ofcompounds which are suitable for use in a fluorescent or phosphorescentOLED, in particular a phosphorescent OLED, in particular as matrixmaterial or as electron-transport or hole-blocking material.

Levy et al., Bull. Soc. Chim. Fr. 1987, 1, 193-198, describe thesynthesis of certain unsubstituted indolobenzothiophene derivatives.However, the electroluminescence properties of the compounds or a use ofthe compounds as functional materials in electronic devices are notdisclosed.

It has now been found that compounds of the formula (I) which werehitherto not known in the prior art are eminently suitable for use asfunctional materials in electronic devices, in particular as matrixmaterials for phosphorescent dopants. On use of the compounds accordingto the invention, higher efficiencies and longer lifetimes canpreferably be achieved than with materials in accordance with the priorart.

The present invention thus relates to a compound of the followingformula (I)

where the following applies to the symbols and indices occurring:

-   X¹, X², X³ are on each occurrence, identically or differently,    C(R²)₂, C═O, C═NR², Si(R²)₂, NR¹, PR¹, P(═O)R¹, O, S, S═O or S(═O)₂;-   Z is on each occurrence, identically or differently, CR² or N, where    not more than two adjacent groups Z may simultaneously be equal to    N;-   R¹ is on each occurrence, identically or differently, C(═O)R³,    CR³═C(R³)₂, C(═O)OR³, C(═O)NR³ ₂, P(═O)(R³)₂, OR³, S(═O)R³,    S(═O)₂R³, or an aromatic or heteroaromatic ring system having 5 to    60 aromatic ring atoms, which may in each case be substituted by one    or more radicals R³, or a combination of these systems, where two or    more radicals R¹ may be linked to one another and may form an    aliphatic or aromatic ring;-   R² is on each occurrence, identically or differently, H, D, F, Cl,    Br, I, B(OR³)₂, CHO, C(═O)R³, CR³═C(R³)₂, CN, C(═O)OR³, C(═O)NR³ ₂,    Si(R³)₃, N(R³)₂, NO₂, P(═O)(R³)₂, OS(═O)₂R³, OH, S(═O)R³, S(═O)₂R³,    a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C    atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group    having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40    C atoms, where the above-mentioned groups may each be substituted by    one or more radicals R³ and where one or more non-adjacent CH₂    groups in the above-mentioned groups may be replaced by —R³C═CR³—,    —C≡C—, Si(R³)₂, Ge(R³)₂, Sn(R³)₂, C═O, C═S, C═Se, C═NR³, —C(═O)O—,    —C(═O)NR³—, NR³, P(═O)(R³), —O—, —S—, S═O or S(═O)₂ and where one or    more H atoms in the above-mentioned groups may be replaced by D, F,    Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring system    having 5 to 60 aromatic ring atoms, which may in each case be    substituted by one or more radicals R³, or an aryloxy or    heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be    substituted by one or more radicals R³, or a combination of these    systems, where two or more radicals R² may be linked to one another    and may form an aliphatic or aromatic ring;-   R³ is on each occurrence, identically or differently, H, D, F, Cl,    Br, I, B(OR⁴)₂, CHO, C(═O)R⁴, CR⁴═C(R⁴)₂, CN, C(═O)OR⁴, C(═O)NR⁴ ₂,    Si(R⁴)₃, N(R⁴)₂, NO₂, P(═O)(R⁴)₂, OS(═O)₂R⁴, OH, S(═O) R⁴, S(═O)₂R⁴,    a straight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C    atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group    having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40    C atoms, where the above-mentioned groups may each be substituted by    one or more radicals R⁴ and where one or more non-adjacent CH₂    groups in the above-mentioned groups may be replaced by —R⁴C═CR⁴—,    —C≡C—, Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C═O, C═S, C═Se, C═NR⁴, —C(═O)O—,    —C(═O)NR⁴—, NR⁴, P(═O)(R⁴), —O—, —S—, S═O or S(═O)₂ and where one or    more H atoms in the above-mentioned groups may be replaced by D, F,    Cl, Br, I, CN or NO₂, or an aromatic or heteroaromatic ring system    having 5 to 60 aromatic ring atoms, which may in each case be    substituted by one or more radicals R⁴, or an aryloxy or    heteroaryloxy group having 5 to 60 aromatic ring atoms, which may be    substituted by one or more radicals R⁴, or a combination of these    systems, where two or more radicals R³ may be linked to one another    and may form an aliphatic or aromatic ring;-   R⁴ is, identically or differently on each occurrence, H, D, F or an    aliphatic, aromatic and/or heteroaromatic organic radical having 1    to 20 C atoms, in which, in addition, one or more H atoms may be    replaced by D or F; two or more substituents R⁴ here may also be    linked to one another and form an aliphatic or aromatic ring; and-   n has a value of 0, 1 or 2; and    where the case where all groups X¹, X² and X³ are identical is    excluded.

For clarity, it should be noted that the compounds of the formula (I)conform to the following formula (Ia) for n=0, to the following formula(Ib) for n=1 and to the following formula (Ic) for n=2:

In the case of compounds of the formula (Ic), the groups X² occurringmay furthermore be identical or different.

An aryl group in the sense of this invention contains 6 to 60 C atoms; aheteroaryl group in the sense of this invention contains 1 to 60 C atomsand at least one heteroatom, with the proviso that the sum of C atomsand heteroatoms is at least 5. The heteroatoms are preferably selectedfrom N, O and/or S. An aryl group or heteroaryl group here is taken tomean either a simple aromatic ring, i.e. benzene, or a simpleheteroaromatic ring, for example pyridine, pyrimidine, thiophene, etc.,or a condensed (fused) aryl or heteroaryl group, for examplenaphthalene, anthracene, phenanthrene, quinoline, isoquinoline,carbazole, etc.

An aryl or heteroaryl group, which may in each case be substituted bythe above-mentioned radicals R² or R³ and which may be linked to thearomatic or heteroaromatic ring system via any desired positions, istaken to mean, in particular, groups derived from benzene, naphthalene,anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene,fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene,benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene,benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole,isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine,phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline,benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole,imidazole, benzimidazole, naphthimidazole, phenanthrimidazole,pyridimidazole, pyrazinimidazole, quinoxalinimidazole, oxazole,benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole,1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine,pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine,naphthyridine, azacarbazole, benzocarboline, phenanthroline,1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole,1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine,1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine,1,2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pteridine, indolizine andbenzothiadiazole.

An aromatic ring system in the sense of this invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense ofthis invention contains 5 to 60 aromatic ring atoms, at least one ofwhich is a heteroatom. The heteroatoms are preferably selected from N, Oand/or S. An aromatic or heteroaromatic ring system in the sense of thisinvention is intended to be taken to mean a system which does notnecessarily contain only aryl or heteroaryl groups, but instead inwhich, in addition, a plurality of aryl or heteroaryl groups may beconnected by a non-aromatic unit (preferably less than 10% of the atomsother than H), such as, for example, an sp³-hybridised C, Si, N or Oatom, an sp²-hybridised C or N atom or an sp-hybridised C atom. Thus,for example, systems such as 9,9′-spirobifluorene, 9,9′-diarylfluorene,triarylamine, diaryl ether, stilbene, etc., are also intended to betaken to be aromatic ring systems in the sense of this invention, as aresystems in which two or more aryl groups are connected, for example, bya linear or cyclic alkyl, alkenyl or alkynyl group or by a silyl group.Furthermore, systems in which two or more aryl or heteroaryl groups arelinked to one another via one or more single bonds are also taken to bearomatic or heteroaromatic ring systems in the sense of this invention.

An aromatic or heteroaromatic ring system having 5-60 aromatic ringatoms, which may also in each case be substituted by radicals as definedabove and which may be linked to the aromatic or heteroaromatic groupvia any desired positions, is taken to mean, in particular, groupsderived from benzene, naphthalene, anthracene, benzanthracene,phenanthrene, benzophenanthrene, pyrene, chrysene, perylene,fluoranthene, naphthacene, pentacene, benzopyrene, biphenyl,biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene,dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- ortrans-indenofluorene, truxene, isotruxene, spirotruxene,spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,indole, isoindole, carbazole, indolocarbazole, indenocarbazole,pyridine, quinoline, isoquinoline, acridine, phenanthridine,benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,phenothiazine, phenoxazine, pyrazole, indazole, imidazole,benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole,pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole,naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole,1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine,benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene,2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene,4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine,phenothiazine, fluorubin, naphthyridine, azacarbazole, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole or combinations ofthese groups.

For the purposes of the present invention, a straight-chain alkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, inwhich, in addition, individual H atoms or CH₂ groups may be substitutedby the groups mentioned above under the definition of the radicals R²and R³, is preferably taken to mean the radicals methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-methylbutyl,n-pentyl, s-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl,neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl,trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl,propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl,heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl,butynyl, pentynyl, hexynyl or octynyl. An alkoxy or thioalkyl grouphaving 1 to 40 C atoms is preferably taken to mean methoxy,trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,s-butoxy, tbutoxy, n-pentoxy, s-pentoxy, 2-methylbutoxy, n-hexoxy,cyclohexyloxy, n-heptoxy, cycloheptyloxy, n-octyloxy, cyclooctyloxy,2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio,ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio,s-butylthio, t-butylthio, n-pentylthio, spentylthio, n-hexylthio,cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio,cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio,pentafluoroethylthio, 2,2,2-trifluoroethylthio, ethenylthio,propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio,cyclohexenylthio, heptenylthio, cycloheptenylthio, octenylthio,cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio,hexynylthio, heptynylthio or octynylthio.

In a preferred embodiment of the invention, 0, 1 or 2 groups Z peraromatic or heteroaromatic six-membered ring are equal to N. In aparticularly preferred embodiment of the invention, no or precisely onegroup Z per aromatic or heteroaromatic six-membered ring is equal to N.In an even more preferred embodiment of the invention, no group Z isequal to N and all groups Z are equal to CR².

In a further preferred embodiment of the invention, n is equal to 0or 1. In these cases, the compounds according to the invention conformto the formulae (Ia) and (Ib) shown above.

It is furthermore preferred for X¹ to be selected from C(R²)₂, C═O,Si(R²)₂, NR¹, PR¹, P(═O)R¹, O or S. X¹ is very particularly preferablyselected from NR¹, PR¹, P(═O)R¹, O or S.

It is furthermore preferred for X² to be selected on each occurrence,identically or differently, from C(R²)₂, C═O, Si(R²)₂, NR¹, PR¹,P(═O)R¹, O or S. X² is very particularly preferably selected on eachoccurrence, identically or differently, from NR¹, PR¹, P(═O)R¹, O or S.

It is furthermore preferred for X³ to be selected from C(R²)₂, C═O,Si(R²)₂, NR¹, PR¹, P(═O)R¹, O or S. X³ is very particularly preferablyselected from NR¹, PR¹, P(═O)R¹, O or S.

Preferred combinations of the groups X¹ and X³ for compounds of theformula (I) where n=0 (formula (Ia)) are indicated in the followingtable.

X¹ X³ 1 C(R²)₂ C═O 2 C(R²)₂ NR¹ 3 C(R²)₂ PR¹ 4 C(R²)₂ P(═O)R¹ 5 C(R²)₂ O6 C(R²)₂ S 7 C═O C(R²)₂ 8 C═O NR¹ 9 C═O PR¹ 10 C═O P(═O)R¹ 11 C═O O 12C═O S 13 NR¹ C(R²)₂ 14 NR¹ C═O 15 NR¹ PR¹ 16 NR¹ P(═O)R¹ 17 NR¹ O 18 NR¹S 19 PR¹ C(R²)₂ 20 PR¹ C═O 21 PR¹ NR¹ 22 PR¹ P(═O)R¹ 23 PR¹ O 24 PR¹ S25 P(═O)R¹ C(R²)₂ 26 P(═O)R¹ C═O 27 P(═O)R¹ NR¹ 28 P(═O)R¹ PR¹ 29P(═O)R¹ O 30 P(═O)R¹ S 31 O C(R²)₂ 32 O C═O 33 O NR¹ 34 O PR¹ 35 OP(═O)R¹ 36 O S 37 S C(R²)₂ 38 S C═O 39 S NR¹ 40 S PR¹ 41 S P(═O)R¹ 42 SO

Preferred combinations of the groups X¹, X² and X³ for compounds of theformula (I) where n=1 (formula (Ib)) are indicated in the followingtable.

X¹ X² X³ 44 C(R²)₂ C(R²)₂ C═O 45 C(R²)₂ C(R²)₂ NR¹ 46 C(R²)₂ C(R²)₂ PR¹47 C(R²)₂ C(R²)₂ P(═O)R¹ 48 C(R²)₂ C(R²)₂ O 49 C(R²)₂ C(R²)₂ S 50 C(R²)₂C═O C(R²)₂ 51 C(R²)₂ C═O C═O 52 C(R²)₂ C═O NR¹ 53 C(R²)₂ C═O PR¹ 54C(R²)₂ C═O P(═O)R¹ 55 C(R²)₂ C═O O 56 C(R²)₂ C═O S 57 C(R²)₂ NR¹ C(R²)₂58 C(R²)₂ NR¹ C═O 59 C(R²)₂ NR¹ NR¹ 60 C(R²)₂ NR¹ PR¹ 61 C(R²)₂ NR¹P(═O)R¹ 62 C(R²)₂ NR¹ O 63 C(R²)₂ NR¹ S 64 C(R²)₂ PR¹ C(R²)₂ 65 C(R²)₂PR¹ C═O 66 C(R²)₂ PR¹ NR¹ 67 C(R²)₂ PR¹ PR¹ 68 C(R²)₂ PR¹ P(═O)R¹ 69C(R²)₂ PR¹ O 70 C(R²)₂ PR¹ S 71 C(R²)₂ P(═O)R¹ C(R²)₂ 72 C(R²)₂ P(═O)R¹C═O 73 C(R²)₂ P(═O)R¹ NR¹ 74 C(R²)₂ P(═O)R¹ PR¹ 75 C(R²)₂ P(═O)R¹P(═O)R¹ 76 C(R²)₂ P(═O)R¹ O 77 C(R²)₂ P(═O)R¹ S 78 C(R²)₂ O C(R²)₂ 79C(R²)₂ O C═O 80 C(R²)₂ O NR¹ 81 C(R²)₂ O PR¹ 82 C(R²)₂ O P(═O)R¹ 83C(R²)₂ O O 84 C(R²)₂ O S 85 C(R²)₂ S C(R²)₂ 86 C(R²)₂ S C═O 87 C(R²)₂ SNR¹ 88 C(R²)₂ S PR¹ 89 C(R²)₂ S P(═O)R¹ 90 C(R²)₂ S O 91 C(R²)₂ S S 92C═O C(R²)₂ C(R²)₂ 93 C═O C(R²)₂ C═O 94 C═O C(R²)₂ NR¹ 95 C═O C(R²)₂ PR¹96 C═O C(R²)₂ P(═O)R¹ 97 C═O C(R²)₂ O 98 C═O C(R²)₂ S 99 C═O C═O C(R²)₂100 C═O C═O NR¹ 101 C═O C═O PR¹ 102 C═O C═O P(═O)R¹ 103 C═O C═O O 104C═O C═O S 105 C═O NR¹ C(R²)₂ 106 C═O NR¹ C═O 107 C═O NR¹ NR¹ 108 C═O NR¹PR¹ 109 C═O NR¹ P(═O)R¹ 110 C═O NR¹ O 111 C═O NR¹ S 112 C═O PR¹ C(R²)₂113 C═O PR¹ C═O 114 C═O PR¹ NR¹ 115 C═O PR¹ PR¹ 116 C═O PR¹ P(═O)R¹ 117C═O PR¹ O 118 C═O PR¹ S 119 C═O P(═O)R¹ C(R²)₂ 120 C═O P(═O)R¹ C═O 121C═O P(═O)R¹ NR¹ 122 C═O P(═O)R¹ PR¹ 123 C═O P(═O)R¹ P(═O)R¹ 124 C═OP(═O)R¹ O 125 C═O P(═O)R¹ S 126 C═O O C(R²)₂ 127 C═O O C═O 128 C═O O NR¹129 C═O O PR¹ 130 C═O O P(═O)R¹ 131 C═O O O 132 C═O O S 133 C═O S C(R²)₂134 C═O S C═O 135 C═O S NR¹ 136 C═O S PR¹ 137 C═O S P(═O)R¹ 138 C═O S O139 C═O S S 140 NR¹ C(R²)₂ C(R²)₂ 141 NR¹ C(R²)₂ C═O 142 NR¹ C(R²)₂ NR¹143 NR¹ C(R²)₂ PR¹ 144 NR¹ C(R²)₂ P(═O)R¹ 145 NR¹ C(R²)₂ O 146 NR¹C(R²)₂ S 147 NR¹ C═O C(R²)₂ 148 NR¹ C═O C═O 149 NR¹ C═O NR¹ 150 NR¹ C═OPR¹ 151 NR¹ C═O P(═O)R¹ 152 NR¹ C═O O 153 NR¹ C═O S 154 NR¹ NR¹ C(R²)₂155 NR¹ NR¹ C═O 156 NR¹ NR¹ PR¹ 157 NR¹ NR¹ P(═O)R¹ 158 NR¹ NR¹ O 159NR¹ NR¹ S 160 NR¹ PR¹ C(R²)₂ 161 NR¹ PR¹ C═O 162 NR¹ PR¹ NR¹ 163 NR¹ PR¹PR¹ 164 NR¹ PR¹ P(═O)R¹ 165 NR¹ PR¹ O 166 NR¹ PR¹ S 167 NR¹ P(═O)R¹C(R²)₂ 168 NR¹ P(═O)R¹ C═O 169 NR¹ P(═O)R¹ NR¹ 170 NR¹ P(═O)R¹ PR¹ 171NR¹ P(═O)R¹ P(═O)R¹ 172 NR¹ P(═O)R¹ O 173 NR¹ P(═O)R¹ S 174 NR¹ O C(R²)₂175 NR¹ O C═O 176 NR¹ O NR¹ 177 NR¹ O PR¹ 178 NR¹ O P(═O)R¹ 179 NR¹ O O180 NR¹ O S 181 NR¹ S C(R²)₂ 182 NR¹ S C═O 183 NR¹ S NR¹ 184 NR¹ S PR¹185 NR¹ S P(═O)R¹ 186 NR¹ S O 187 NR¹ S S 188 PR¹ C(R²)₂ C(R²)₂ 189 PR¹C(R²)₂ C═O 190 PR¹ C(R²)₂ NR¹ 191 PR¹ C(R²)₂ PR¹ 192 PR¹ C(R²)₂ P(═O)R¹193 PR¹ C(R²)₂ O 194 PR¹ C(R²)₂ S 195 PR¹ C═O C(R²)₂ 196 PR¹ C═O C═O 197PR¹ C═O NR¹ 198 PR¹ C═O PR¹ 199 PR¹ C═O P(═O)R¹ 200 PR¹ C═O O 201 PR¹C═O S 202 PR¹ NR¹ C(R²)₂ 203 PR¹ NR¹ C═O 204 PR¹ NR¹ NR¹ 205 PR¹ NR¹ PR¹206 PR¹ NR¹ P(═O)R¹ 207 PR¹ NR¹ O 208 PR¹ NR¹ S 209 PR¹ PR¹ C(R²)₂ 210PR¹ PR¹ C═O 211 PR¹ PR¹ NR¹ 212 PR¹ PR¹ P(═O)R¹ 213 PR¹ PR¹ O 214 PR¹PR¹ S 215 PR¹ P(═O)R¹ C(R²)₂ 216 PR¹ P(═O)R¹ C═O 217 PR¹ P(═O)R¹ NR¹ 218PR¹ P(═O)R¹ PR¹ 219 PR¹ P(═O)R¹ P(═O)R¹ 220 PR¹ P(═O)R¹ O 221 PR¹P(═O)R¹ S 222 PR¹ O C(R²)₂ 223 PR¹ O C═O 224 PR¹ O NR¹ 225 PR¹ O PR¹ 226PR¹ O P(═O)R¹ 227 PR¹ O O 228 PR¹ O S 229 PR¹ S C(R²)₂ 230 PR¹ S C═O 231PR¹ S NR¹ 232 PR¹ S PR¹ 233 PR¹ S P(═O)R¹ 234 PR¹ S O 235 PR¹ S S 236P(═O)R¹ C(R²)₂ C(R²)₂ 237 P(═O)R¹ C(R²)₂ C═O 238 P(═O)R¹ C(R²)₂ NR¹ 239P(═O)R¹ C(R²)₂ PR¹ 240 P(═O)R¹ C(R²)₂ P(═O)R¹ 241 P(═O)R¹ C(R²)₂ O 242P(═O)R¹ C(R²)₂ S 243 P(═O)R¹ C═O C(R²)₂ 244 P(═O)R¹ C═O C═O 245 P(═O)R¹C═O NR¹ 246 P(═O)R¹ C═O PR¹ 247 P(═O)R¹ C═O P(═O)R¹ 248 P(═O)R¹ C═O O249 P(═O)R¹ C═O S 250 P(═O)R¹ NR¹ C(R²)₂ 251 P(═O)R¹ NR¹ C═O 252 P(═O)R¹NR¹ NR¹ 253 P(═O)R¹ NR¹ PR¹ 254 P(═O)R¹ NR¹ P(═O)R¹ 255 P(═O)R¹ NR¹ O256 P(═O)R¹ NR¹ S 257 P(═O)R¹ PR¹ C(R²)₂ 258 P(═O)R¹ PR¹ C═O 259 P(═O)R¹PR¹ NR¹ 260 P(═O)R¹ PR¹ PR¹ 261 P(═O)R¹ PR¹ P(═O)R¹ 262 P(═O)R¹ PR¹ O263 P(═O)R¹ PR¹ S 264 P(═O)R¹ P(═O)R¹ C(R²)₂ 265 P(═O)R¹ P(═O)R¹ C═O 266P(═O)R¹ P(═O)R¹ NR¹ 267 P(═O)R¹ P(═O)R¹ PR¹ 268 P(═O)R¹ P(═O)R¹ O 269P(═O)R¹ P(═O)R¹ S 270 P(═O)R¹ O C(R²)₂ 271 P(═O)R¹ O C═O 272 P(═O)R¹ ONR¹ 273 P(═O)R¹ O PR¹ 274 P(═O)R¹ O P(═O)R¹ 275 P(═O)R¹ O O 276 P(═O)R¹O S 277 P(═O)R¹ S C(R²)₂ 278 P(═O)R¹ S C═O 279 P(═O)R¹ S NR¹ 280 P(═O)R¹S PR¹ 281 P(═O)R¹ S P(═O)R¹ 282 P(═O)R¹ S O 283 P(═O)R¹ S S 284 O C(R²)₂C(R²)₂ 285 O C(R²)₂ C═O 286 O C(R²)₂ NR¹ 287 O C(R²)₂ PR¹ 288 O C(R²)₂P(═O)R¹ 289 O C(R²)₂ O 290 O C(R²)₂ S 291 O C═O C(R²)₂ 292 O C═O C═O 293O C═O NR¹ 294 O C═O PR¹ 295 O C═O P(═O)R¹ 296 O C═O O 297 O C═O S 298 ONR¹ C(R²)₂ 299 O NR¹ C═O 300 O NR¹ NR¹ 301 O NR¹ PR¹ 302 O NR¹ P(═O)R¹303 O NR¹ O 304 O NR¹ S 305 O PR¹ C(R²)₂ 306 O PR¹ C═O 307 O PR¹ NR¹ 308O PR¹ PR¹ 309 O PR¹ P(═O)R¹ 310 O PR¹ O 311 O PR¹ S 312 O P(═O)R¹ C(R²)₂313 O P(═O)R¹ C═O 314 O P(═O)R¹ NR¹ 315 O P(═O)R¹ PR¹ 316 O P(═O)R¹P(═O)R¹ 317 O P(═O)R¹ O 318 O P(═O)R¹ S 319 O O C(R²)₂ 320 O O C═O 321 OO NR¹ 322 O O PR¹ 323 O O P(═O)R¹ 324 O O S 325 O S C(R²)₂ 326 O S C═O327 O S NR¹ 328 O S PR¹ 329 O S P(═O)R¹ 330 O S O 331 O S S 332 S C(R²)₂C(R²)₂ 333 S C(R²)₂ C═O 334 S C(R²)₂ NR¹ 335 S C(R²)₂ PR¹ 336 S C(R²)₂P(═O)R¹ 337 S C(R²)₂ O 338 S C(R²)₂ S 339 S C═O C(R²)₂ 340 S C═O C═O 341S C═O NR¹ 342 S C═O PR¹ 343 S C═O P(═O)R¹ 344 S C═O O 345 S C═O S 346 SNR¹ C(R²)₂ 347 S NR¹ C═O 348 S NR¹ NR¹ 349 S NR¹ PR¹ 350 S NR¹ P(═O)R¹351 S NR¹ O 352 S NR¹ S 353 S PR¹ C(R²)₂ 354 S PR¹ C═O 355 S PR¹ NR¹ 356S PR¹ PR¹ 357 S PR¹ P(═O)R¹ 358 S PR¹ O 359 S PR¹ S 360 S P(═O)R¹ C(R²)₂361 S P(═O)R¹ C═O 362 S P(═O)R¹ NR¹ 363 S P(═O)R¹ PR¹ 364 S P(═O)R¹P(═O)R¹ 365 S P(═O)R¹ O 366 S P(═O)R¹ S 367 S O C(R²)₂ 368 S O C═O 369 SO NR¹ 370 S O PR¹ 371 S O P(═O)R¹ 372 S O O 373 S O S 374 S S C(R²)₂ 375S S C═O 376 S S NR¹ 377 S S PR¹ 378 S S P(═O)R¹ 379 S S O

Preferred embodiments of the compounds of the formula (Ia) according tothe invention furthermore conform to the following formulae (Ia-1) to(Ia-10)

where the groups Z and R¹ are as defined above.

Preferred embodiments of the compounds of the formula (Ib) according tothe invention furthermore conform to the following formulae (Ib-1) to(Ib-20)

where the groups Z and R¹ are as defined above.

It is furthermore preferred in accordance with the invention for atleast one of the groups X¹, X² and X³ to represent a group NR¹.

It is furthermore preferred for compounds of the formula (I) where n=1for the groups X¹ and X³ to be identical.

It is again furthermore preferred for the compounds of the formulae(Ia-1) to (Ia-10) and (1b-1) to (Ib-20) for Z to be equal to CR².

In a further preferred embodiment of the invention, R¹ is on eachoccurrence, identically or differently, an aromatic or heteroaromaticring system having 5 to 30 aromatic ring atoms, which may in each casebe substituted by one or more radicals R³.

In a particularly preferred embodiment of the invention, R¹ is anaromatic or heteroaromatic ring system having 5 to 30 aromatic ringatoms, which may in each case be substituted by one or more radicals R³.

It is furthermore preferred for the compounds for use in theelectroluminescent devices according to the invention to carry, assubstituent R¹ or R², at least one group which is selected fromelectron-deficient heteroaryl groups, aromatic or heteroaromatic ringsystems having 10 to 30 aromatic ring atoms and from arylamine groups,where the above-mentioned group may be substituted by one or more of theabove-mentioned radicals.

The above-mentioned electron-deficient heteroaryl groups here arepreferably selected from pyridine, pyrimidine, pyridazine, pyrazine,triazine and benzimidazole, each of which may be substituted by one ormore of the radicals defined above.

The above-mentioned aromatic or heteroaromatic ring systems having 10 to30 aromatic ring atoms are preferably selected from naphthyl,anthracenyl, phenanthrenyl, benzanthracenyl, pyrenyl, biphenyl,terphenyl and quaterphenyl, each of which may be substituted by one ormore of the radicals defined above.

The above-mentioned arylamine groups are preferably groups of thefollowing formula (A)

where the symbol * marks the bond to the remainder of the compound andfurthermore

Ar¹, Ar², Ar³ represent, identically or differently on each occurrence,an aryl or heteroaryl group having 5 to 20 aromatic ring atoms, whichmay in each case be substituted by one or more radicals R³ or R⁴,

Ar² and Ar³ may be linked to one another by a single bond, and

q is equal to 0, 1, 2, 3, 4 or 5.

In a further preferred embodiment of the invention, R² is on eachoccurrence, identically or differently, H, D, F, C(═O)R³, CN, Si(R³)₃,N(R³)₂, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms ora branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms or analkenyl or alkynyl group having 2 to 10 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR³ and where one or more non-adjacent CH₂ groups in the above-mentionedgroups may be replaced by —R³C═CR³—, —C≡C—, Si(R³)₂, C═O, —C(═O)O—,—C(═O)NR³—, NR³, —O— or —S— and where one or more H atoms in theabove-mentioned groups may be replaced by D, F or CN, or an aromatic orheteroaromatic ring system having 5 to 30 aromatic ring atoms, which mayin each case be substituted by one or more radicals R³, or an aryloxy orheteroaryloxy group having 5 to 30 aromatic ring atoms, which may besubstituted by one or more radicals R³, where two or more radicals R²may be linked to one another and may form an aliphatic or aromatic ring.

In the above-mentioned case where two or more radicals R² are connectedto one another, it is preferred for the two radicals to be a constituentof a moiety

from formula (I) where Z is equal to CR². It is furthermore explicitlypreferred for two radicals R² which are bonded to two adjacent C atomson the aromatic or heteroaromatic six-membered ring to be connected toone another, for example in the following manner:

It is furthermore preferred in this case for the connection of the twogroups to form a condensed aryl or heteroaryl group which has 4 to 8aromatic ring atoms more than the original aryl or heteroaryl group.

In a further preferred embodiment of the invention, the two radicals R²of a group X¹, X² or X³, which corresponds to C(R²)₂, are connected toone another and form an aliphatic or aromatic ring. Preferredembodiments thereof are, inter alia, an aliphatic three-membered ring,four-membered ring, five-membered ring or six-membered ring, as depictedin the following formula. In the formula, the group X optionally standsfor X¹, X² or X³. The said rings may be substituted by one or more ofthe above-mentioned radicats and/or condensed onto further rings.

In a further preferred embodiment of the invention, R³ is on eachoccurrence, identically or differently, H, D, F, C(═O)R⁴, CN, Si(R⁴)₃,N(R⁴)₂, a straight-chain alkyl or alkoxy group having 1 to 10 C atoms ora branched or cyclic alkyl or alkoxy group having 3 to 10 C atoms or analkenyl or alkynyl group having 2 to 10 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR⁴ and where one or more non-adjacent CH₂ groups in the above-mentionedgroups may be replaced by —R⁴C═CR⁴—, —C≡C—, Si(R⁴)₂, C═O, —C(═O)O—,—C(═O)NR⁴—, NR⁴, —O— or —S— and where one or more H atoms in theabove-mentioned groups may be replaced by D, F or CN, or an aromatic orheteroaromatic ring system having 5 to 30 aromatic ring atoms, which mayin each case be substituted by one or more radicals R⁴, or an aryloxy orheteroaryloxy group having 5 to 30 aromatic ring atoms, which may besubstituted by one or more radicals R⁴, where two or more radicals R³may be linked to one another and may form an aliphatic or aromatic ring.

Examples of compounds according to the invention are shown below.

The compounds of the formula (I) according to the invention can beprepared by known organochemical synthetic processes. These include, forexample, bromination, Suzuki coupling and Hartwig-Buchwald coupling,inter alia.

The person skilled in the art in the area of organic synthesis and inthe area of functional materials for organic electroluminescent deviceswill be able to deviate from the illustrative synthetic routes shownbelow and/or modify individual steps in a suitable manner if such actionis advantageous.

Compounds according to the invention which contain two five-memberedheteroaromatic rings which are condensed with one another can beobtained, for example, by the synthetic route shown in Scheme 1.

To this end, firstly an organometallic coupling reaction, preferably aSuzuki reaction, is carried out between a benzothiophene derivative oran analogous compound, such as, for example, a benzofuran derivative,and a nitrophenyl derivative. The nitro group is subsequently reduced,and a ring-closure reaction commences in which the second condensed-onfive-membered heteroaromatic ring is formed as a pyrrole ring. Thenitrogen atom of the pyrrole ring can finally be arylated in aHartwig-Buchwald coupling.

Compounds according to the invention which contain three five-memberedheteroaromatic rings which are condensed with one another canfurthermore be obtained, for example, by the synthetic route shown inScheme 2. This route likewise proceeds via a nitroaryl intermediate,which supplies the skeleton of the compounds according to the inventionhaving three condensed five-membered aromatic rings via reduction andring closure.

As an alternative to the route shown above, compounds according to theinvention which contain three five-membered heteroaromatic rings whichare condensed with one another can also be synthesised by the routeshown in Scheme 3.

Starting from a benzothiophene derivative, a benzofuran derivative or ananalogous compound, firstly an organometallic coupling reaction,preferably a Suzuki coupling, is carried out with a second correspondingheteroaryl compound. A double bromination, for example using elementalbromine, is subsequently carried out in the two positions in theα-position to the bond between the two heteroaryl groups. Finally, thethird central heteroaromatic five-membered ring is closed by aHartwig-Buchwald coupling to a primary arylamine or heteroarylamine.

The present invention thus furthermore relates to a process for thepreparation of a compound of the formula (I), characterised in that oneor more condensed heteroaromatic five-membered rings are formed by aring-closure reaction.

The compounds according to the invention described above, in particularcompounds which are substituted by reactive leaving groups, such asbromine, iodine, boronic acid or boronic acid ester, can be used asmonomers for the preparation of corresponding oligomers, dendrimers orpolymers. The oligomerisation or polymerisation here is preferablycarried out via the halogen functionality or the boronic acidfunctionality.

The invention therefore furthermore relates to oligomers, polymers ordendrimers comprising one or more compounds of the formula (I), wherethe bond(s) to the polymer, oligomer or dendrimer may be localised atany desired positions in formula (I) substituted by R¹ or R². Dependingon the linking of the compound of the formula (I), the compound is partof a side chain of the oligomer or polymer or part of the main chain. Anoligomer in the sense of this invention is taken to mean a compoundwhich is built up from at least three monomer units. A polymer in thesense of the invention is taken to mean a compound which is built upfrom at least ten monomer units. The polymers, oligomers or dendrimersaccording to the invention may be conjugated, partially conjugated ornon-conjugated. The oligomers or polymers according to the invention maybe linear, branched or dendritic. In the structures linked in a linearmanner, the units of the formula (I) may be linked directly to oneanother or linked to one another via a divalent group, for example via asubstituted or unsubstituted alkylene group, via a heteroatom or via adivalent aromatic or heteroaromatic group. In branched and dendriticstructures, three or more units of the formula (I) may, for example, belinked via a trivalent or polyvalent group, for example via a trivalentor polyvalent aromatic or heteroaromatic group, to give a branched ordendritic oligomer or polymer.

The same preferences as described above for compounds of the formula (I)apply to the recurring units of the formula (I) in oligomers, dendrimersand polymers.

For the preparation of the oligomers or polymers, the monomers accordingto the invention are homopolymerised or copolymerised with furthermonomers. Suitable and preferred comonomers are selected from fluorenes(for example in accordance with EP 842208 or WO 00/22026),spirobifluorenes (for example in accordance with EP 707020, EP 894107 orWO 06/061181), para-phenylenes (for example in accordance with WO92/18552), carbazoles (for example in accordance with WO 04/070772 or WO04/113468), thiophenes (for example in accordance with EP 1028136),dihydrophenanthrenes (for example in accordance with WO 05/014689 or WO07/006,383), cis- and trans-indenofluorenes (for example in accordancewith WO 04/041901 or WO 04/113412), ketones (for example in accordancewith WO 05/040302), phenanthrenes (for example in accordance with WO05/104264 or WO 07/017,066) or also a plurality of these units. Thepolymers, oligomers and dendrimers usually also contain further units,for example emitting (fluorescent or phosphorescent) units, such as, forexample, vinyltriarylamines (for example in accordance with WO07/068325) or phosphorescent metal complexes (for example in accordancewith WO 06/003000), and/or charge-transport units, in particular thosebased on triarylamines.

The polymers, oligomers and dendrimers according to the invention haveadvantageous properties, in particular long lifetimes, high efficienciesand good colour coordinates.

The polymers and oligomers according to the invention are generallyprepared by polymerisation of one or more types of monomer, at least onemonomer of which results in recurring units of the formula (I) in thepolymer. Suitable polymerisation reactions are known to the personskilled in the art and are described in the literature. Particularlysuitable and preferred polymerisation reactions which result in C—C orC—N links are the following:

(A) SUZUKI polymerisation;(B) YAMAMOTO polymerisation;(C) STILLE polymerisation; and(D) HARTWIG-BUCHWALD polymerisation.

The way in which the polymerisation can be carried out by these methodsand the way in which the polymers can then be separated off from thereaction medium and purified is known to the person skilled in the artand is described in detail in the literature, for example in WO2003/048225, WO 2004/037887 and WO 2004/037887.

The present invention thus also relates to a process for the preparationof the polymers, oligomers and dendrimers according to the invention,which is characterised in that they are prepared by SUZUKIpolymerisation, YAMAMOTO polymerisation, STILLE polymerisation orHARTWIG-BUCHWALD polymerisation. The dendrimers according to theinvention can be prepared by processes known to the person skilled inthe art or analogously thereto. Suitable processes are described in theliterature, such as, for example, in Frechet, Jean M. J.; Hawker, CraigJ., “Hyperbranched polyphenylene and hyperbranched polyesters: newsoluble, three-dimensional, reactive polymers”, Reactive & FunctionalPolymers (1995), 26(1-3), 127-36; Janssen, H. M.; Meijer, E. W., “Thesynthesis and characterization of dendritic molecules”, MaterialsScience and Technology (1999), 20 (Synthesis of Polymers), 403-458;Tomalia, Donald A., “Dendrimer molecules”, Scientific American (1995),272(5), 62-6; WO 02/067343 A1 and WO 2005/026144 A1.

The processing of the compounds according to the invention from theliquid phase, for example by spin coating or by printing processes,requires formulations of the compounds according to the invention. Theseformulations can be, for example, solutions, dispersions ormini-emulsions. It may be preferred to use mixtures of two or moresolvents for this purpose. Suitable and preferred solvents are, forexample, toluene, anisole, o-, m- or p-xylene, methyl benzoate,dimethylanisole, mesitylene, tetralin, veratrol, THF, methyl-THF, THP,chlorobenzene, dioxane or mixtures of these solvents.

The invention therefore furthermore relates to a formulation, inparticular a solution, dispersion or mini-emulsion, comprising at leastone compound of the formula (I) or at least one polymer, oligomer ordendrimer containing at least one unit of the formula (I) and at leastone solvent, preferably an organic solvent. The way in which solutionsof this type can be prepared is known to the person skilled in the artand is described, for example, in WO 2002/072714, WO 2003/019694 and theliterature cited therein.

The compounds of the formula (I) according to the invention are suitablefor use in electronic devices, in particular in organicelectroluminescent devices (OLEDs). Depending on the substitution, thecompounds are employed in various functions and layers.

For example, compounds of the formula (I) which containelectron-deficient groups, such as six-membered ring heteroaryl groupshaving one or more nitrogen atoms or five-membered ring heteroarylgroups having two or more nitrogen atoms, are particularly suitable foruse as matrix material for phosphorescent dopants, as electron-transportmaterial or as hole-blocking material.

Furthermore, compounds of the formula (I) which are substituted byaromatic ring systems, in particular by aromatic ring systems having 12to 30 aromatic ring atoms, and/or by one or more arylamino groups areparticularly suitable for use as hole-transport materials or for use asfluorescent dopants.

The compounds according to the invention are preferably employed aselectron-transport material in an electron-transport layer, as matrixmaterial in an emitting layer or as hole-transport material in ahole-transport layer. However, they can also be employed in other layersand/or functions, for example as fluorescent dopants in an emittinglayer or as hole- or electron-blocking materials.

The invention therefore furthermore relates to the use of the compoundsof the formula (I) according to the invention in electronic devices. Theelectronic devices here are preferably selected from the groupconsisting of organic integrated circuits (O-ICs), organic field-effecttransistors (O-FETs), organic thin-film transistors (O-TFTs), organiclight-emitting transistors (O-LETs), organic solar cells (O-SCs),organic optical detectors, organic photoreceptors, organic field-quenchdevices (O-FQDs), light-emitting electrochemical cells (LECs), organiclaser diodes (O-lasers) and particularly preferably selected fromorganic electroluminescent devices (OLEDs).

The invention again furthermore relates to electronic devices comprisingat least one compound of the formula (I). The electronic devices hereare preferably selected from the devices mentioned above. Particularpreference is given to organic electroluminescent devices comprising ananode, a cathode and at least one emitting layer, characterised in thatat least one organic layer, which may be an emitting layer, anelectron-transport layer or another layer, comprises at least onecompound of the formula (I).

Apart from the cathode, anode and emitting layer, the organicelectroluminescent device may also comprise further layers. These areselected, for example, from in each case one or more hole-injectionlayers, hole-transport layers, hole-blocking layers, electron-transportlayers, electron-injection layers, electron-blocking layers,exciton-blocking layers, charge-generation layers (IDMC 2003, Taiwan;Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N.Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having ChargeGeneration Layer), coupling-out layers and/or organic or inorganic p/njunctions. However, it should be pointed out that each of these layersdoes not necessarily have to be present and the choice of layers isalways dependent on the compounds used and in particular also on whetherthe electroluminescent device is fluorescent or phosphorescent.

The organic electroluminescent device may also comprise a plurality ofemitting layers. These emission layers in this case particularlypreferably have in total a plurality of emission maxima between 380 nmand 750 nm, resulting overall in white emission, i.e. various emittingcompounds which are able to fluoresce or phosphoresce and which emitblue and yellow, orange or red light are used in the emitting layers.Particular preference is given to three-layer systems, i.e. systemshaving three emitting layers, where one or more of these layers maycomprise at least one compound of the formula (I) and where the threelayers exhibit blue, green and orange or red emission (for the basicstructure see, for example, WO 05/011013). Likewise suitable in suchsystems for white emission are emitters which have broad-band emissionbands and thus exhibit white emission. Alternatively and/oradditionally, the compounds according to the invention may also bepresent in a hole-transport layer or electron-transport layer or inanother layer in such systems.

It is preferred in accordance with the invention if the compound of theformula (I) is employed in an electronic device comprising one or morephosphorescent dopants. The compound here can be used in various layers,preferably in an electron-transport layer, a hole-transport layer, ahole-injection layer or in the emitting layer.

However, the compound of the formula (I) can also be employed inaccordance with the invention in an electronic device comprising one ormore fluorescent dopants and no phosphorescent dopants.

Suitable phosphorescent dopants (=triplet emitters) are, in particular,compounds which emit light, preferably in the visible region, onsuitable excitation and in addition contain at least one atom having anatomic number greater than 20, preferably greater than 38 and less than84, particulaxly preferably greater than 56 and less than 80. Thephosphorescent diopants used are preferably compounds which containcopper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium,iridium, palladium, platinum, silver, gold or europium, in particularcompounds which contain iridium, platinum or copper.

For the purposes of the present invention, all luminescent iridium,platinum or copper complexes are regarded as phosphorescent compounds.

Examples of the phosphorescent dopants described above are revealed bythe applications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP 1191612, EP 1191614, WO 05/033244, WO 05/019373 and US2005/0258742. In general, all phosphorescent complexes as used inaccordance with the prior art for phosphorescent OLEDs and as are knownto the person skilled in the art in the area of organicelectroluminescent devices are suitable. The person skilled in the artwill also be able to employ further phosphorescent complexes withoutinventive step in combination with the compounds of the formula (I)according to the invention in organic electroluminescent devices.

Further examples of suitable phosphorescent dopants are revealed by thetable in a later section.

In a preferred embodiment of the present invention, the compounds of theformula (I) are employed as matrix material in combination with one ormore dopants, preferably phosphorescent dopants.

A dopant is taken to mean the component whose proportion in the mixtureis the smaller in a system comprising a matrix material and a dopant.Correspondingly, a matrix material is taken to mean the component whoseproportion in the mixture is the greater in a system comprising a matrixmaterial and a dopant.

The proportion of the matrix material in the emitting layer is in thiscase between 50.0 and 99.9% by vol., preferably between 80.0 and 99.5%by vol. and particularly preferably between 92.0 and 99.5% by vol. forfluorescent emitting layers and between 85.0 and 97.0% by vol. forphosphorescent emitting layers.

Correspondingly, the proportion of the dopant is between 0.1 and 50.0%by vol., preferably between 0.5 and 20.0% by vol. and particularlypreferably between 0.5 and 8.0% by vol. for fluorescent emitting layersand between 3.0 and 15.0% by vol. for phosphorescent emitting layers.

An emitting layer of an organic electroluminescent device may alsocomprise systems comprising a plurality of matrix materials(mixed-matrix systems) and/or a plurality of dopants. In this case too,the dopants are generally the materials whose proportion in the systemis the smaller and the matrix materials are the materials whoseproportion in the system is the greater. In individual cases, however,the proportion of an individual matrix material in the system may besmaller than the proportion of an individual dopant.

In a preferred embodiment of the invention, the compounds of the formula(I) are used as a component of mixed-matrix systems. The mixed-matrixsystems preferably comprise two or three different matrix materials,particularly preferably two different matrix materials. Preferably, oneof the two materials here is a material having hole-transportingproperties and the other material is a material havingelectron-transporting properties. The two different matrix materialshere may be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1,particularly preferably 1:10 to 1:1 and very particularly preferably 1:4to 1:1.

The mixed-matrix systems may comprise one or more dopants. The dopantcompound or the dopant compounds together have, in accordance with theinvention, a proportion of 0.1 to 50.0% by vol. in the mixture as awhole and preferably a proportion of 0.5 to 20.0% by vol. in the mixtureas a whole. Correspondingly, the matrix components together have aproportion of 50.0 to 99.9% by vol. in the mixture as a whole andpreferably a proportion of 80.0 to 99.5% by vol. in the mixture as awhole.

Mixed-matrix systems are preferably employed in phosphorescent organicelectroluminescent devices.

Particularly suitable matrix materials, which can be employed incombination with the compounds according to the invention as matrixcomponents of a mixed-matrix system, are aromatic ketones, aromaticphosphine oxides or aromatic sulfoxides or sulfones, for example inaccordance with WO 04/013080, WO 04/093207, WO 06/005627 or WO10/006680, triarylamines, carbazole derivatives, for exampleCBP(N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed inWO 05/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO08/086,851, indolocarbazole derivatives, for example in accordance withWO 07/063,754 or WO 08/056746, azacarbazole derivatives, for example inaccordance with EP 1617710, EP 1617711, EP 1731584, JP 2005/347160,bipolar matrix materials, for example in accordance with WO 07/137,725,silanes, for example in accordance with WO 05/111172, azaboroles orboronic esters, for example in accordance with WO 06/117052, triazinederivatives, for example in accordance with WO 10/015,306, WO 07/063,754or WO 08/056746, zinc complexes, for example in accordance with EP652273 or WO 09/062,578, diazasilole or tetraazasilole derivatives, forexample in accordance with WO 10/054,729, diazaphosphole derivatives,for example in accordance with WO 10/054,730, indenocarbazolederivatives, for example in accordance with WO 2010/136109 and WO2011/000455, or bridged carbazoles, for example in accordance with theunpublished applications DE 102010005697.9 and DE 102010014933.0.

Preferred phosphorescent dopants for use in mixed-matrix systemscomprising the compounds according to the invention are thephosphorescent dopants mentioned in the above table.

In a further preferred embodiment of the invention, the compounds of theformula (I) are employed as hole-transport material. The compounds arethen preferably employed in a hole-transport layer and/or in ahole-injection layer. A hole-injection layer in the sense of thisinvention is a layer which is directly adjacent to the anode. Ahole-transport layer in the sense of this invention is a layer which islocated between the hole-injection layer and the emission layer. If thecompounds of the formula (I) are used as hole-transport material, it maybe preferred for them to be doped with electron-acceptor compounds, forexample with F₄-TCNQ or with compounds as described in EP 1476881 or EP1596445.

In a further preferred embodiment of the invention, a compound of theformula (I) is used as hole-transport material in combination with ahexaazatriphenylene derivative, as described in US 2007/0092755. Thehexaazatriphenylene derivative is particularly preferably employed inits own layer here.

If the compound of the formula (I) is employed as hole-transportmaterial in a hole-transport layer, the compound can be employed as purematerial, i.e. in a proportion of 100%, in the hole-transport layer orit can be employed in combination with further compounds in thehole-transport layer.

In a further embodiment of the invention, the compounds of the formula(I) are employed as fluorescent dopants in an emitting layer. Inparticular, the compounds are suitable as fluorescent dopants if theyare substituted by one or more aromatic systems, preferably aromaticsystems containing 12 to 30 aromatic ring atoms. The compounds accordingto the invention are preferably used as green or blue emitters.

The proportion of the compound of the formula (I) as dopant in themixture of the emitting layer is in this case between 0.1 and 50.0% byvol., preferably between 0.5 and 20.0% by vol., particularly preferablybetween 0.5 and 8.0% by vol. Correspondingly, the proportion of thematrix material is between 50.0 and 99.9% by vol., preferably between80.0 and 99.5% by vol., particularly preferably between 92.0 and 99.5%by vol.

Preferred matrix materials for use in combination with the compoundsaccording to the invention as fluorescent dopants are mentioned in oneof the following sections. They correspond to the matrix materials forfluorescent dopants that are indicated as preferred.

In a further embodiment of the invention, the compounds are employed aselectron-transport materials in an electron-transport layer of anorganic electroluminescent device. In this case, it is preferred for thecompounds according to the invention to have one or moreelectron-deficient groups, such as, for example, six-membered heteroarylring groups containing one or more, nitrogen atoms or five-memberedheteroaryl ring groups containing two or more nitrogen atoms.

The electron-transport layer in the electroluminescent devices accordingto the invention may be doped. Suitable dopants are alkali metals oralkalimetal compounds, such as, for example, Liq (lithium quinolinate).In a preferred embodiment of the invention, the electron-transport layeris, in particular, doped if the electron-transport material is abenzimidazole derivative or a triazine derivative. The preferred dopantis then Liq.

It is furthermore a subject-matter of the present invention that thecompounds according to the invention are employed as hole-blockingmaterial. The compounds are then preferably employed in a hole-blockinglayer, in particular in a phosphorescent OLED. A hole-blocking layer inthe sense of this invention is a layer which is arranged between anemitting layer and an electron-transport layer.

The further functional materials preferably employed in the electronicdevices comprising one or more compounds according to the invention areshown below.

Particularly suitable phosphorescent dopants are the compounds shown inthe following table.

Preferred fluorescent dopants are selected from the class of thearylamines. An arylamine or aromatic amine in the sense of thisinvention is taken to mean a compound which contains three substitutedor unsubstituted aromatic or heteroaromatic ring systems bonded directlyto the nitrogen. At least one of these aromatic or heteroaromatic ringsystems is preferably a condensed ring system, particularly preferablyhaving at least 14 aromatic ring atoms. Preferred examples thereof arearomatic anthracenamines, aromatic anthracenediamines, aromaticpyrenamines, aromatic pyrenediamines, aromatic chrysenamines or aromaticchrysenediamines. An aromatic anthracenamine is taken to mean a compoundin which one diarylamino group is bonded directly to an anthracenegroup, preferably in the 9-position. An aromatic anthracenediamine istaken to mean a compound in which two diarylamino groups are bondeddirectly to an anthracene group, preferably in the 9,10-position.Aromatic pyrenamines, pyrenediamines, chrysenamines and chrysenediaminesare defined analogously thereto, where the diarylamino groups arepreferably bonded to the pyrene in the 1-position or in the1,6-position. Further preferred fluorescent dopants are selected fromindenofluorenamines or indenofluorenediamines, for example in accordancewith WO 06/122630, benzoindenofluorenamines orbenzoindenofluorenediamines, for example in accordance with WO08/006,449, and dibenzoindenofluorenamines ordibenzoindenofluorenediamines, for example in accordance with WO07/140,847. Examples of fluorescent dopants from the class of thestyrylamines are substituted or unsubstituted tristilbenamines or thefluorescent dopants described in WO 06/000388, WO 06/058737, WO06/000389, WO 07/065,549 and WO 07/115,610. Preference is furthermoregiven to the condensed hydrocarbons disclosed in DE 102008035413.

Furthermore, the compounds of the formula (I) are preferably used asfluorescent dopants.

Suitable fluorescent dopants are furthermore the structures depicted inthe following table, and the derivatives of these structures disclosedin JP 06/001973, WO 04/047499, WO 06/098080, WO 07/065678, US2005/0260442 and WO 04/092111.

Suitable matrix materials, preferably for fluorescent dopants, arematerials from various classes of substance. Preferred matrix materialsare selected from the classes of the oligoarylenes (for example2,2′,7,7′-tetraphenylspirobifluorene in accordance with EP 676461 ordinaphthylanthracene), in particular the oligoarylenes containingcondensed aromatic groups, the oligoarylenevinylenes (for example DPVBior spiro-DPVBi in accordance with EP 676461), the polypodal metalcomplexes (for example in accordance with WO 04/081017), thehole-conducting compounds (for example in accordance with WO 04/058911),the electron-conducting compounds, in particular ketones, phosphineoxides, sulfoxides, etc. (for example in accordance with WO 05/084081and WO 05/084082), the atropisomers (for example in accordance with WO06/048268), the boronic acid derivatives (for example in accordance withWO 06/117052) or the benzanthracenes (for example in accordance with WO08/145,239). Suitable matrix materials are furthermore preferably thecompounds according to the invention. Particularly preferred matrixmaterials are selected from the classes of the oligoarylenes; comprisingnaphthalene, anthracene, benzanthracene and/or pyrene or atropisomers ofthese compounds, the oligoarylenevinylenes, the ketones, the phosphineoxides and the sulfoxides. Very particularly preferred matrix materialsare selected from the classes of the oligoarylenes, comprisinganthracene, benzanthracene, benzophenanthrene and/or pyrene oratropisomers of these compounds. An oligoarylene in the sense of thisinvention is intended to be taken to mean a compound in which at leastthree aryl or arylene groups are bonded to one another.

Suitable matrix materials, preferably for fluorescent dopants, are, forexample, the materials depicted in the following table, and derivativesof these materials, as disclosed in WO 04/018587, WO 08/006,449, U.S.Pat. No. 5,935,721, US 2005/0181232, JP 2000/273056, EP 681019, US2004/0247937 and US 2005/0211958.

Besides the compounds of the formula (I), suitable charge-transportmaterials, as can be used in the hole-injection or hole-transport layeror in the electron-transport layer of the organic electroluminescentdevice according to the invention, are, for example, the compoundsdisclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010, orother materials as are employed in these layers in accordance with theprior art.

The cathode of the organic electroluminescent device preferablycomprises metals having a low work function, metal alloys ormultilayered structures comprising various metals, such as, for example,alkaline-earth metals, alkali metals, main-group metals or lanthanoids(for example Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Also suitable arealloys comprising an alkali metal or alkaline-earth metal and silver,for example an alloy comprising magnesium and silver. In the case ofmultilayered structures, further metals which have a relatively highwork function, such as, for example, Ag or Al, can also be used inaddition to the said metals, in which case combinations of the metals,such as, for example, Ca/Ag, Ba/Ag or Mg/Ag, are generally used. It mayalso be preferred to introduce a thin interlayer of a material having ahigh dielectric constant between a metallic cathode and the organicsemiconductor. Suitable for this purpose are, for example, alkali metalfluorides or alkaline-earth metal fluorides, but also the correspondingoxides or carbonates (for example LiF, Li₂O, BaF₂, MgO, NaF, CsF,Cs₂CO₃, etc.). Furthermore, lithium quinolinate (LiQ) can be used forthis purpose. The layer thickness of this layer is preferably between0.5 and 5 nm.

The anode preferably comprises materials having a high work function.The anode preferably has a work function of greater than 4.5 eV vs.vacuum. Suitable for this purpose are on the one hand metals having ahigh redox potential, such as, for example, Ag, Pt or Au. On the otherhand, metal/metal oxide electrodes (for example Al/Ni/NiO_(x),Al/PtO_(x)) may also be preferred. For some applications, at least oneof the electrodes must be transparent or partially transparent in orderto facilitate either irradiation of the organic material (organic solarcells) or the coupling-out of light (OLEDs, O-lasers). Preferred anodematerials here are conductive mixed metal oxides. Particular preferenceis given to indium tin oxide (ITO) or indium zinc oxide (IZO).Preference is furthermore given to conductive, doped organic materials,in particular conductive, doped polymers.

The device is appropriately (depending on the application) structured,provided with contacts and finally sealed, since the lifetime of thedevices according to the invention is shortened in the presence of waterand/or air.

In a preferred embodiment, the organic electroluminescent deviceaccording to the invention is characterised in that one or more layersare applied by means of a sublimation process, in which the materialsare applied by vapour deposition in vacuum sublimation units at aninitial pressure of less than 10⁻⁵ mbar, preferably less than 10⁻⁶ mbar.However, it is also possible here for the initial pressure to be evenlower, for example less than 10⁻⁷ mbar.

Preference is likewise given to an organic electroluminescent device,characterised in that one or more layers are applied by means of theOVPD (organic vapour phase deposition) process or with the aid ofcarriergas sublimation, in which the materials are applied at a pressureof between 10⁻⁵ mbar and 1 bar. A special case of this process is theOVJP (organic vapour jet printing) process, in which the materials areapplied directly through a nozzle and are thus structured (for exampleM. S. Arnold et al., Appl. Phys. Lett. 2008, 92, 053301).

Preference is furthermore given to an organic electroluminescent device,characterised in that one or more layers are produced from solution,such as, for example, by spin coating, or by means of any desiredprinting process, such as, for example, screen printing, flexographicprinting, nozzle printing or offset printing, but particularlypreferably LITI (light induced thermal imaging, thermal transferprinting) or ink-jet printing. Soluble compounds of the formula (I) arenecessary for this purpose. High solubility can be achieved throughsuitable substitution of the compounds.

For the production of an organic electroluminescent device according tothe invention, it is furthermore preferred to apply one or more layersfrom solution and one or more layers by a sublimation process.

The organic electroluminescent devices comprising one or more compoundsof the formula (I) can be employed in accordance with the invention indisplays, as light sources in lighting applications and as light sourcesin medical and/or cosmetic applications (for example light therapy).

On use of the compounds of the formula (I) in organic electroluminescentdevices, one or more of the advantages indicated below can be achieved:

The compounds of the formula (I) are very highly suitable for use asmatrix materials for phosphorescent dopants and also highly suitable foruse as electron-transport materials. On use of the compounds accordingto the invention in these functions, good power efficiencies, lowoperating voltages and good lifetimes of the organic electroluminescentdevices are obtained.

Furthermore, the compounds of the formula (I) are distinguished by highoxidation stability in solution, which has an advantageous effect duringpurification and handling of the compounds and on use thereof inelectronic devices.

Furthermore, the compounds of the formula (I) are temperature-stable andcan thus be sublimed substantially without decomposition. Purificationof the compounds is thus simplified, and the compounds can be obtainedin higher purity, which has a positive effect on the performance data ofthe electronic devices comprising the materials. In particular, deviceshaving longer operating lifetimes can thus be produced.

The invention is explained in greater detail by the following workingexamples, without wishing it to be restricted thereby.

USE EXAMPLES A) Synthesis Examples

The following syntheses are carried out, unless indicated otherwise,under a protective-gas atmosphere in dried solvents. Benzo[b]thiopheneand solvents can be purchased commercially, for example from ALDRICH.

1) Synthesis of compound 1:6-o-Biphenylbis[1]-benzothieno[2,3-b:3′,2′-d]-pyrrole Scheme for theSynthesis of Compounds 1 and 2

Step 1-a: 3-Bromobenzo[b]thiophene

100 g (745 mmol) of benzo[b]thiophene are suspended in 1000 ml ofchloroform and 1000 ml of glacial acetic acid with 145 g (815 mmol) ofNBS and stirred at room temperature for 24 h. After a TLC check, thebatch is evaporated under reduced pressure. The purification is carriedout by distillation of the product and gives a red oil (111 g; 73%).

Step 1-b: [3,3]-Bisbenzo[b]thiophenyl

3000 ml of THF, 40 g (61 mmol) of bis(triphenylphosphine)nickel(II)chloride, 34.3 g (524.6 mmol) of zinc and 101.6 g (275 mmol) of n-Bu₄NIare added to 50 g (235 mmol) of the compound from the preceding step.The batch is heated at 70° C. for 20 h, then cooled to room temperature,and 400 ml of water are added. The mixture is extracted with ethylacetate, the combined organic phases are then dried over sodium sulfateand evaporated under reduced pressure. The purification is carried outby recrystallisation (heptane/MeOH) and gives a white solid (22 g, 71.7mmol, 61%).

Step 1-c: 2,2′-Dibromo-[3,3′]-bisbenzo[b]thiophenyl

10 g (37.5 mmol) of the compound from the preceding step are initiallyintroduced in 250 ml of acetic acid. With exclusion of light, a solutionof 8 ml (24 g, 150 mmol) of Br₂ in 10 ml of acetic acid is addeddropwise at −5° C. The mixture is subsequently allowed to come to roomtemperature and is stirred at this temperature for a further 24 h. 150ml of water are then added to the mixture, which is then extracted withCH₂Cl₂. The organic phase is dried over MgSO₄, and the solvents areremoved in vacuo. The product is washed by stirring with hot hexane andfiltered off with suction. Yield: 14 g (33 mmol), 83.5%. Purityaccording to ¹H-NMR about 98%.

Compound 1: 6-o-Biphenylbis-[1]benzothieno[2,3-b:3′,2′-d]pyrrole

500 ml of toluene, 2.3 g (2.5 mmol) oftris(dibenzylideneacetone)dipalladium, 10 ml of 1M t-Bu₃P in toluene and11.5 g (120 mmol) of sodium tert-butoxide are added to 21.2 g (50 mmol)of the compound from the preceding step. 6.8 g (40 mmol) of2-aminobiphenyl are subsequently added. The batch is heated at 110° C.for 20 h, then cooled to room temperature, and 400 ml of water areadded. The mixture is extracted with ethyl acetate, the combined organicphases are then dried over sodium sulfate and evaporated under reducedpressure. The residue is recrystallised from toluene and fromdichloromethane/isopropanol and finally sublimed in a high vacuum. Thepurity is 99.9%. The yield is 10.6 g (24.5 mmol), corresponding to 49%of theory.

2) Synthesis of compound 2:2,4,6-Trimethylphenylbis[1]benzothieno-[2,3-b:3′,2′-d]pyrrole

500 ml of toluene, 2.3 g (2.5 mmol) oftris(dibenzylideneacetone)dipalladium, 10 ml of 1M t-Bu₃P in toluene and11.5 g (120 mmol) of sodium tert-butoxide are added to 21.2 g (50 mmol)of the compound from step 1-c. 5.4 g (40 mmol) of 2,4,6-trimethylanilineare subsequently added. The batch is heated at 110° C. for 20 h, thencooled to room temperature, and 400 ml of water are added. The mixtureis extracted with ethyl acetate, the combined organic phases are thendried over sodium sulfate and evaporated under reduced pressure. Theresidue is recrystallised from toluene and from heptane/methanol andfinally sublimed in a high vacuum. The purity is 99.9%. The yield is11.5 g (29 mmol), corresponding to 58% of theory.

3) Synthesis of compound 3:2,4,6-Triphenylpyrimidinylbis[1]-benzothieno-[2,3-b:3′,2′-d]pyrroleScheme for the Synthesis of Compound 3

Step 3-a: 2-Nitro-3,3′-bisbenzo[b]thiophene

12.6 g (47 mmol) of 3,3′-dibenzo[b]thiophene are initially introduced in1000 ml of glacial acetic acid. The batch is warmed to a bathtemperature of 60° C., and a mixture of 4 ml of conc. HNO₃ and 200 ml ofglacial acetic acid is added. The mixture is subsequently stirred at 65°C. for 1 h and poured into ice-water. The yellow solid formed in theprocess is filtered off with suction. The product is washed by stirringwith hot hexane and filtered off with suction. Yield: 13.5 g (43 mmol),96% of theory, purity according to ¹H-NMR about 98%.

Step 3-b: 6H-Bis[1]benzothieno[2,3-b:3′,2′-d]pyrrole

11.7 g (42 mmol) of the compound from the preceding step and 29 ml (165mmol) of triethyl phosphite are dissolved in 350 ml of1,2-dichlorobenzene and stirred at 150° C. for 24 h. After cooling, thesolvent is distilled off. The purification is carried out byrecrystallisation (heptane) and gives a colourless solid (3.5 g, 12.6mmol, 30%). Purity according to ¹H-NMR about 90%.

Step 3-c: 5-Bromo-2,4,6-triphenylpyrimidine

50 g (177 mmol) of trifluoromethanesulfonic anhydride and 36.5 g (354mmol) of benzonitrile are dissolved in 300 ml of dichloromethane. Asolution of dichloromethane and 35.2 g (177 mmol) of 2-bromoacetophenoneis added dropwise to this solution at room temperature. The reactionmixture is left to stir at RT for 24 h. The batch is washed with aqueousNaHCO₃ solution, and the organic phase is dried using MgSO₄ andevaporated to dryness in a rotary evaporator. The product is washed bystirring with hot ethanol and filtered off with suction. Yield: 33.5 g(86.5 mmol), 49% of theory, purity according to ¹H-NMR about 98%.

Compound 3:2,4,6-Triphenylpyrimidinylbis[1]benzothieno[2,3-b:3′,2′-d]-pyrrole

9.1 g (23.5 mmol) of the compound from the preceding step, 13.11 g (47mmol) of 6H-bis[1]benzothieno[2,3-b:3′,2′-d]pyrrole and 29.2 g of Rb₂CO₃are suspended in 250 ml of p-xylene. 0.95 g (4.2 mmol) of Pd(OAc)₂ and12.6 ml of a 1M tri-tert-butylphosphine solution are added to thissuspension. The reaction mixture is heated under reflux for 24 h. Aftercooling, the organic phase is separated off, washed three times with 200ml of water and subsequently evaporated to dryness. The residue isextracted with hot toluene, recrystallised three times from toluene andfinally sublimed in a high vacuum, giving 5.6 g (9.7 mmol) of theproduct, corresponding to 41% of theory. The purity is 99.9%.

4) Synthesis of compound 4:3-((Z)-Buta-1,3-dienyl)-1-[3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-2-methyl-1H-benzo[4,5]thieno[2,3-b]pyrroleScheme for the Synthesis of Compound 4

Step 4-a:2-Benzo[b]thiophen-3-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

1600 ml of THF, 145 g (568 mmol) of bis(pinacolato)diborane and 142 g(1.45 mol) of potassium acetate are added to 111 g (516 mmol) of3-bromobenzo[b]thiophene. 10 g (12 mmol) of1,1-bis(diphenylphosphino)ferrocenepalladium(II) chloride (complex withdichloromethane (1:1), Pd 13%) are subsequently added. The batch isheated at 70° C. for 16 h, then cooled to room temperature, and 400 mlof water are added. The mixture is extracted with ethyl acetate, thecombined organic phases are then dried over sodium sulfate andevaporated under reduced pressure. The purification is carried out byrecrystallisation (heptane/MeOH) and gives a brown solid (78 g, 58.3%).

Step 4-b: 2-Nitrophenylbenzo[b]thiophene

56 g (0.225 mol) of the compound from the preceding step, 70.2 g (1.2molar equivalents, 0.270 mol) of 1-iodonitrobenzene and 286 g (1.345mol) of tripotassium phosphate are suspended in 700 ml of toluene, 700ml of dioxane and 700 ml of water. 0.684 g (2.25 mmol) oftri-o-tolylphosphine and then 2.53 g (11.2 mmol) of palladium(II)acetate are added to this suspension, and the reaction mixture is heatedunder reflux for 21 h. After cooling, the organic phase is separatedoff. The aqueous phase is extracted with dichloromethane, the combinedorganic phases are then dried over sodium sulfate, filtered andevaporated under reduced pressure. The residue is chromatographed oversilica gel. The yield is 39 g (152 mmol), corresponding to 68% oftheory.

Step 4-c: 6H-0 penzothieno[2,3-b]indole

32 g (0.124 mol) of the compound from the preceding step and 86 ml(0.495 mol) of triethyl phosphite are dissolved in 1000 ml of1,2-dichlorobenzene and stirred at 150° C. for 72 h. After cooling, thesolvent is distilled off. The purification is carried out byrecrystallisation (heptane) and gives a colourless solid (12 g, 45.3%).

Compound 4:3-((Z)-Buta-1,3-dienyl)-1-[3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl]-2-methyl-1H-benzo[4,5]thieno[2,3-b]pyrrole

9.1 g (23.5 mmol) of 5-bromo-2,4,6-triphenylpyrimidine, 13.11 g (47mmol) of 6H-[1]benzothieno[2,3-b]indole and 29.2 g of Rb₂CO₃ aresuspended in 250 ml of p-xylene. 0.95 g (4.2 mmol) of Pd(OAc)₂ and 12.6ml of a 1M tri-tert-butylphosphine solution are added to thissuspension. The reaction mixture is heated under reflux for 24 h. Aftercooling, the organic phase is separated off, washed three times with 200ml of water and subsequently evaporated to dryness. The residue isextracted with hot toluene and recrystallised three times from tolueneand finally sublimed in a high vacuum, giving 5.6 g (9.7 mmol)corresponding to 41% of theory, the purity is 99.9%.

5) Synthesis of Compound 5 Scheme for the Synthesis of Compound 5

Step 5-a: 5-Bromobenzo[b]thiophene

97.2 g (351 mmol) of 1-bromo-4-[(2,2-dimethoxyethyl)sulfanyl]benzene and100 g of polyphosphoric acid are dissolved in 2000 ml of chlorobenzeneand stirred at 135° C. for 4 h. After cooling, the solvent is distilledoff. The residue is extracted with dichloromethane, and the organicphase is washed three times with 200 ml of water. The combined organicphases are then dried over sodium sulfate, filtered and evaporated underreduced pressure. The purification is carried out by recrystallisation(heptane) and gives a colourless solid (60.3 g, 283 mmol, 80.1%).

Step 5-b: Benzo[b]thiophene-5-carbonitrile

45 g (211 mmol) of the compound from the preceding step, 26.18 g (295mmol) of copper(I) cyanide and 25 ml of pyridine are dissolved in 500 mlof N,N-dimethylformamide and stirred at 130° C. for 24 h. After cooling,the solvent is distilled off. The residue is extracted withdichloromethane, and the organic phase is washed three times with 200 mlof water. The combined organic phases are then dried over sodiumsulfate, filtered and evaporated under reduced pressure. The residue ischromatographed over silica gel. The purification is carried out byrecrystallisation (heptane) and gives a colourless solid (18.9 g, 118.2mmol, 56%).

Step 5-c: 3-Bromo-1-benzothiophene-6-carbonitrile

23.7 g (149 mmol) of the compound from the preceding step are suspendedin 200 ml of chloroform and 200 ml of glacial acetic acid with 29 g (163mmol) of NBS and stirred at RT for 24 hrs. After a TLC check, the batchis evaporated under reduced pressure. The purification is carried out bydistillation of the product and gives a red oil (12.5 g, 52.15 mmol, 35%of theory).

Step 5-d

16.4 g (56.25 mmol) of 3-bromo-1-benzothiophene-6-carbonitrile, 17.55 g(67.5 mmol) of2-benzo[b]thiophen-3-yl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and 71.5g (6.0 molar equivalents, 0.335 mol) of tripotassium phosphate aresuspended in 500 ml of toluene, 500 ml of dioxane and 250 ml of water.0.180 g (0.56 mmol) of tri-o-tolylphosphine and then 0.63 g (2.8 mmol)of palladium(II) acetate are added to this suspension, and the reactionmixture is heated under reflux for 24 h. After cooling, the organicphase is separated off. The aqueous phase is extracted withdichloromethane, the combined organic phases are then dried over sodiumsulfate, filtered and evaporated under reduced pressure. The residue ischromatographed over silica gel. The yield is 7.4 g (25.3 mmol),corresponding to 45% of theory.

Step 5-e

11.06 g (37.5 mmol) of the compound from the preceding step is initiallyintroduced in 250 ml of acetic acid. A solution of 8 ml (24 g, 150 mmol)of Br₂ in 10 ml of acetic acid is subsequently added dropwise withexclusion of light at −5° C., the mixture is allowed to come to RT andis stirred further at this temperature for 24 h. 150 ml of water arethen added to the mixture, which is then extracted with CH₂Cl₂. Theorganic phase is dried over MgSO₄, and the solvents are removed invacuo. The product is washed by stirring with hot hexane and filteredoff with suction. Yield: 10.11 g (22.5 mmol), 60.5% of theory, purityaccording to ¹H-NMR about 98%.

Step 5-f

200 ml of toluene are added to 8.98 g (20 mmol) of the compound from thepreceding step, 0.95 g (1 mmol) oftris(dibenzylideneacetone)dipalladium, 4 ml of 1M t-Bu₃P solution intoluene and 4.6 g (48 mmol) of sodium tert-butoxide. 1.8 g (16 mmol) ofaniline are subsequently added. The batch is heated at 110° C. for 20 h,then cooled to room temperature, and 100 ml of water are added. Themixture is extracted with ethyl acetate, the combined organic phases arethen dried over sodium sulfate and evaporated under reduced pressure.The residue is recrystallised from toluene and from heptane/methanol.The yield is 3.3 g (8.64 mmol), corresponding to 48% of theory. Purityaccording to ¹H-NMR about 96%.

Compound 5

Ethanol (50 ml) and sodium hydroxide solution (20 ml) are added to 3.3 g(8.64 mmol) of the compound from the preceding step. The reactionmixture is stirred under reflux for 6 h. After cooling to 25° C., thesolution is evaporated in vacuo. 50 ml of 5M HCl are subsequently addedslowly. The precipitated solid is filtered off and washed with water.The yield is 3.1 g (7.8 mmol), corresponding to 91% of theory. Purityaccording to ¹H-NMR about 95%.

Thionyl chloride (50 ml) is added to the carboxylic acid obtained (3.1g, 7.8 mmol). The reaction mixture is warmed to 80° C. and heated underreflux for 2 h. The solvent is then removed in vacuo. The carboxylicacid chloride is obtained in a yield of 2.9 g (7.7 mmol, 98% of theory).

1.0 g (7.6 mmol) of aluminium trichloride, 2.9 g (7.7 mmol) of thecarboxylicacid chloride, 0.18 ml (2.3 mmol) of thionyl chloride and 1.6ml (15.8 mmol) of benzonitrile are dissolved in 80 ml of1,2-dichlorobenzene. The batch is firstly warmed to 110° C., and 0.8 g(15.2 mmol) of ammonium chloride is then added. The batch issubsequently heated at 110° C. for 20 h, then cooled to roomtemperature, and 100 ml of methanol are added. The solid is filtered offwith suction and washed with ethanol. The residue is chromatographedover silica gel, extracted with hot toluene, recrystallised three timesfrom toluene and finally sublimed in a high vacuum, giving 2.2 g (3.9mmol), corresponding to 29% of theory. The purity is 99.9%.

B) Device Examples

OLEDs according to the invention and OLEDs in accordance with the priorart are produced by a general process in accordance with WO 04/058911,which is adapted to the circumstances described here (layer-thicknessvariation, materials).

In Examples V1 to E8 below (see Tables 1 and 2), the data for variousOLEDs are presented. Glass plates coated with structured ITO (indium tinoxide) in a thickness of 150 nm are coated with 20 nm of PEDOT(poly(3,4-ethylenedioxy-2,5-thiophene), applied by spin coating fromwater; purchased from H. C. Starck, Goslar, Germany) for improvedprocessing. These coated glass plates form the substrates to which theOLEDs are applied. The OLEDs basically have the following layerstructure: substrate/hole-transport layer (HTL)/interlayer(IL)/electron-blocking layer (EBL)/emission layer (EML)/optionalhole-blocking layer (HBL)/electron-transport layer (ETL) and finally acathode. The cathode is formed by an aluminium layer with a thickness of100 nm. The precise structure of the OLEDs is shown in Table 1. Thematerials required for the production of the OLEDs are shown in Table 3.

All materials are applied by thermal vapour deposition in a vacuumchamber. The emission layer here always consists of at least one matrixmaterial (host material) and an emitting dopant (emitter), to which thematrix material or materials is (are) admixed by co-evaporation in acertain proportion by volume. An expression such asST1:HTM4:TEG1(30%:60%:10%) here means that the material ST1 is presentin the layer in a proportion by volume of 30%, HTM4 is present in thelayer in a proportion of 60% and TEG1 is present in the layer in aproportion of 10%. Analogously, the electron-transport layer may alsoconsist of a mixture of two materials.

The OLEDs are characterised by standard methods. To this end, theelectroluminescence spectra, the current efficiency (measured in cd/A),the power efficiency (measured in lm/W) and the external quantumefficiency (EQE, measured in percent) as a function of the luminousdensity, calculated from current/voltage/luminous density characteristiclines (IUL characteristic lines), and the lifetime are determined. Theelectroluminescence spectra are determined at a luminous density of 1000cd/m², and the CIE 1931 x and y colour coordinates are calculatedtherefrom. The expression U1000 in Table 2 denotes the voltage requiredfor a luminous density of 1000 cd/m². CE1000 and PE1000 denote thecurrent and power efficiency respectively which are achieved at 1000cd/m². Finally, EQE1000 is the external quantum efficiency at anoperating luminous density of 1000 cd/m². The lifetime LT is defined asthe time after which the luminous density has dropped from the initialluminous density L0 to a certain proportion L1 on operation at constantcurrent. The expression L0=4000 cd/m² and L1=80% in Table 2 means thatthe lifetime indicated in column LT corresponds to the time after whichthe initial luminous density of the corresponding OLED has dropped from4000 cd/m² to 3200 cd/m². The values for the lifetime can be convertedinto a value for other initial luminous densities with the aid ofconversion formulae known to the person skilled in the art. The lifetimefor an initial luminous density of 1000 cd/m² is the usual figure quotedhere.

The data for the various OLEDs are summarised in Table 2. Examples V1and V2 are comparative examples in accordance with the prior art, whileExamples E1 to E8 show data for OLEDs comprising materials according tothe invention.

Some of the examples are explained in greater detail below in order toillustrate the advantages of the compounds according to the invention.However, it should be pointed out that this only represents a selectionof the data shown in Table 2.

Use of Compounds According to the Invention as Hole-Transport orElectron-Blocking Materials

On use of materials HTM1 and HTM2 in accordance with the prior art ingreen-phosphorescent OLEDs, good efficiency and also operating voltageare obtained. However, the lifetime on use of the compounds is veryshort (Ex. V1, V2). By contrast, with materials HTM3 and HTM4 accordingto the invention, good efficiency and voltage are likewise obtained, buta good lifetime is also obtained (Ex. E1, E2).

Use of Compounds According to the Invention as Matrix Materials inPhosphorescent OLEDs

If materials HTM3 and HTM4 according to the invention are used as secondcomponent in a mixed matrix, good efficiency, lifetime and also voltageare obtained (Ex. E3, E4).

Furthermore, the triazine- or pyrimidine-substituted compounds M2-M4according to the invention can also be employed as individual matrixmaterials, where good efficiencies, lifetimes and operating voltages areagain obtained (Ex. E5 to E8).

TABLE 1 Structure of the OLEDs HTL IL EBL HBL Thick- Thick- Thick- EMLThick- ETL Ex. ness ness ness Thickness ness Thickness V1 SpA1 HATCNHTM1 IC1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm 30 nm 10nm 30 nm V2 SpA1 HATCN HTM2 IC1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 70nm 5 nm 90 nm 30 nm 10 nm 30 nm E1 SpA1 HATCN HTM3 IC1:TEG1 (90%:10%)ST1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm 30 nm 10 nm 30 nm E2 SpA1 HATCNHTM4 IC1:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm 30 nm 10nm 30 nm E3 SpA1 HATCN BPA1 ST1:HTM3:TEG1 — ST1:LiQ (50%:50%) 70 nm 5 nm90 nm (30%:60%:10%) 30 nm 30 nm E4 SpA1 HATCN BPA1 ST1:HTM4:TEG1 —ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm (30%:60%:10%) 30 nm 30 nm E5 SpA1HATCN BPA1 M2:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm 30nm 10 nm 30 nm E6 SpA1 HATCN BPA1 M3:TEG1 (90%:10%) ST1 ST1:LiQ(50%:50%) 70 nm 5 nm 90 nm 30 nm 10 nm 30 nm E7 SpA1 HATCN BPA1 M3:TEG1(90%:10%) — ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm 30 nm 30 nm E8 SpA1 HATCNBPA1 M4:TEG1 (90%:10%) ST1 ST1:LiQ (50%:50%) 70 nm 5 nm 90 nm 30 nm 10nm 30 nm

TABLE 2 Data for the OLEDs CIE x/y L0 U1000 CE1000 PE1000 EQE at 1000(cd/ L1 LT Ex. (V) (cd/A) (lm/W) 1000 cd/m² m²) % (h) V1 3.7 54 46 14.9%0.36/0.60 4000 80 45 V2 3.9 48 39 13.4% 0.36/0.60 4000 80 30 E1 3.6 4943 13.6% 0.36/0.60 4000 80 360 E2 3.8 56 46 15.4% 0.36/0.60 4000 80 385E3 3.9 52 42 14.4% 0.37/0.61 4000 80 460 E4 3.8 54 45 15.1% 0.37/0.614000 80 480 E5 3.7 47 40 13.0% 0.36/0.60 4000 80 340 E6 3.4 54 50 15.5%0.37/0.59 4000 80 305 E7 3.5 56 51 15.7% 0.38/0.59 4000 80 280 E8 3.5 5347 14.8% 0.36/0.60 4000 80 260

TABLE 3 Structural formulae of the materials for the OLEDs

HATCN

SpA1

ST1

BPA1

LiQ

TEG1

IC1

HTM1

HTM2

HTM3

HTM4

M2

M3

M4

1-14. (canceled)
 15. A compound of the formula (I)

where the following applies to the symbols and indices occurring: X¹, X²and X³ are on each occurrence, identically or differently, C(R²)₂, C═O,C═NR², Si(R²)₂, NR¹, PR¹, P(═O)R¹, O, S, S═O or S(═O)₂; Z is on eachoccurrence, identically or differently, CR² or N, where not more thantwo adjacent groups Z may simultaneously be equal to N; R¹ is on eachoccurrence, identically or differently, C(═O)R³, CR³═C(R³)₂, C(═O)OR³,C(═O)NR³ ₂, P(═O)(R³)₂, OR³, S(═O)R³, S(═O)₂R³, or an aromatic orheteroaromatic ring system having 5 to 60 aromatic ring atoms, whichoptionally in each case be substituted by one or more radicals R³, or acombination of these systems, where two or more radicals R¹ isoptionally linked to one another and may form an aliphatic or aromaticring; R² is on each occurrence, identically or differently, H, D, F, Cl,Br, I, B(OR³)₂, CHO, C(═O)R³, CR³═C(R³)₂, CN, C(═O)OR³, C(═O)NR³ ₂,Si(R³)₃, N(R³)₂, NO₂, P(═O)(R³)₂, OS(═O)₂R³, OH, S(═O)R³, S(═O)₂R³, astraight-chain alkyl, alkoxy or thioalkyl group having 1 to 40 C atomsor a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms, where theabove-mentioned groups may each be substituted by one or more radicalsR³ and where one or more non-adjacent CH₂ groups in the above-mentionedgroups is optionally replaced by —R³C═CR³—, —C≡C—, Si(R³)₂, Ge(R³)₂,Sn(R³)₂, C═O, C═S, C═Se, C═NR³, —C(═O)O—, —C(═O)NR³—, NR³, P(═O)(R³),—O—, —S—, S═O or S(═O)₂ and where one or more H atoms in theabove-mentioned groups is optionally replaced by D, F, Cl, Br, I, CN orNO₂, or an aromatic or heteroaromatic ring system having 5 to 60aromatic ring atoms, which may in each case be substituted by one ormore radicals R³, or an aryloxy or heteroaryloxy group having 5 to 60aromatic ring atoms, which is optionally substituted by one or moreradicals R³, or a combination of these systems, where two or moreradicals R² is optionally linked to one another and may form analiphatic or aromatic ring; R³ is on each occurrence, identically ordifferently, H, D, F, Cl, Br, I, B(OR⁴)₂, CHO, C(═O)R⁴, CR⁴═C(R⁴)₂, CN,C(═O)OR⁴, C(═O)NR⁴ ₂, Si(R⁴)₃, N(R⁴)₂, NO₂, P(═O)(O₂, OS(═O)₂R⁴, OH,S(═O)R⁴, S(═O)₂R⁴, a straight-chain alkyl, alkoxy or thioalkyl grouphaving 1 to 40 C atoms or a branched or cyclic alkyl, alkoxy orthioalkyl group having 3 to 40 C atoms or an alkenyl or alkynyl grouphaving 2 to 40 C atoms, where the above-mentioned groups may each besubstituted by one or more radicals R⁴ and where one or morenon-adjacent CH₂ groups in the above-mentioned groups is optionallyreplaced by —R⁴C═CR⁴—, —C≡C—, Si(R⁴)₂, Ge(R⁴)₂, Sn(R⁴)₂, C═O, C═S, C═Se,C═NR⁴, —C(═O)O—, —C(═O)NR⁴—, NR⁴, P(═O)(R⁴), —O—, —S—, S═O or S(═O)₂ andwhere one or more H atoms in the above-mentioned groups is optionallyreplaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic or heteroaromaticring system having 5 to 60 aromatic ring atoms, which may in each casebe substituted by one or more radicals R⁴, or an aryloxy orheteroaryloxy group having 5 to 60 aromatic ring atoms, which isoptionally substituted by one or more radicals R⁴, or a combination ofthese systems, where two or more radicals R³ is optionally linked to oneanother and may form an aliphatic or aromatic ring; R⁴ is, identicallyor differently on each occurrence, H, D, F or an aliphatic, aromaticand/or heteroaromatic organic radical having 1 to 20 C atoms, in which,in addition, one or more H atoms is optionally replaced by D or F; twoor more substituents R⁴ here may also be linked to one another and forman aliphatic or aromatic ring; and n has a value of 0, 1 or 2; where thecase where all groups X¹, X² and X³ are identical is excluded.
 16. Thecompound according to claim 15, wherein n is equal to 0 or
 1. 17. Thecompound according to claim 15, wherein at least one of the groups X′,X² and X³ represents a group NR¹.
 18. The compound according to claim15, wherein 0, 1 or 2 groups Z per aromatic or heteroaromaticsix-membered ring are equal to N.
 19. The compound according to claim15, wherein the groups X¹, X² and X³ are selected, identically ordifferently, from C(R²)₂, C═O, Si(R²)₂, NR¹, PR¹, P(═O)R¹, O and S. 20.The compound according to claim 15, wherein R¹ represents on eachoccurrence, identically or differently, an aromatic or heteroaromaticring system having 5 to 30 aromatic ring atoms, which optionally in eachcase be substituted by one or more radicals R³.
 21. The compoundaccording to claim 15, wherein at least one group is present assubstituent R¹ or R² which is selected from electron-deficientheteroaryl groups, aromatic or heteroaromatic ring systems having 10 to30 aromatic ring atoms and from arylamine groups, each of which isoptionally substituted by one or more radicals as defined in claim 15.22. The compound according to claim 15, wherein the compound conforms toone of the following formulae

where the groups Z and R¹ are as defined in claim
 15. 23. A process forthe preparation of the compound of the formula (I) according to claim15, which comprises ring-closure reacting one or more condensedheteroaromatic five-membered rings.
 24. An oligomer, polymer ordendrimer comprising one or more compounds of the formula (I) accordingto claim 15, where the bond(s) to the polymer, oligomer or dendrimer isoptionally localised at any position in formula (I) substituted by R¹ orR².
 25. A formulation comprising at least one compound of the formula(I) according to claim 15 and at least one solvent.
 26. A formulationcomprising at least one one polymer, oligomer or dendrimer according toclaim 24 and at least one solvent.
 27. An electronic device comprisingthe compound according to claim
 15. 28. An electronic device comprisingthe polymer, oligomer or dendrimer according to claim
 24. 29. An organicelectroluminescent device (OLED) comprising the compound according toclaim
 15. 30. The Electronic device according to claim 27, wherein inthe device is an organic integrated circuit, an organic field-effecttransistor, an organic thin-film transistor, an organic light-emittingtransistor, an organic solar cell, an organic optical detector, anorganic photoreceptor, an organic field-quench device, a light-emittingelectrochemical cell, an organic laser diode or an organicelectroluminescent device.
 31. An organic electroluminescent devicewhich comprises the compound according to claim 15 is employed ashole-transport material in a hole-transport layer or hole-injectionlayer and/or is employed as matrix material in an emitting layer and/oras electron-transport material in an electron-transport layer.
 32. Anorganic electroluminescent device which comprises the polymer, oligomeror dendrimer according to claim 24 is employed as hole-transportmaterial in a hole-transport layer or hole-injection layer and/or isemployed as matrix material in an emitting layer and/or aselectron-transport material in an electron-transport layer.